Catalytic conversion of hydrocarbons



INVENTOR y LEBBEUSCKEM'P r: A IY o. Esa... K VH July 18,' 1944. L. c. KEMP CATALYTIC CONVERSION OF HYDROCARBONS original Filed July 13, 1959 Patented July 18, 1944 cA'rALyTIc CONVERSION or nynaocnaons "Lebbeus C. Kemp, Fishkill, N. Y., assignor, by

mesne assignments,

to The Texas Company,

New York, N. Y., a corporation of Delaware original application July -13, i939, serial No. l 284,192. Divided and this application October A 31,194o,sorial No. 363,589

3 claims. ('cl. 26o-633.15)

l This invention relates to the catalytic conversion oi' unsaturated hydrocarbonsand particuf larly to the catalytic polymerization of normally gaseous olen hydrocarbons forv the production of liquid polymers suitable for'the manufacture of motor fuel.

'Broadlm the invention contemplates effecting Apolymerization of oleiln hydrocarbons during passage through a tower or reaction vessel packed with the catalyst in solid lump or granular form, and wherein the hydrocarbon feed is introduced to the vessel at successive points so as to maintain optimum operating conditions vwithin the vessel. t i

More specifically. the catalytic treatment-is effected inl a tower packed with a catalyst suchias phosphoric acid and having `the catalyst arranged in a plurality of beds spaced a short distancev apart vertically within the vessel. A large portion of the hydrocarbon feed is heated to aD- proximately, or a few degrees below, the reaction temperature, for example, to a temperature of around 375 to 4co F. The heated hydrocarbons are introduced to one end of the vessel, preferably near the top, and caused to flow downwardly within the vessel through the beds of catalyst in succession` Smaller portions of the hydrocarbon feed in an unheated condition, or at temperatures substantially -below the temperature of the hydrocarbons entering the top of the vessel. are introduced at intermediate points between successive beds of the catalyst.

The proportion of hydrocarbon feed introduced at successive points is of such volume and at such temperature as to control, or,if necessary, inhibit substantial rise in the temperature throughout the catalyst massand which rise is due to the exothermic character of the reaction. f

Introduction of the fresh feed at successive points makes up for the reduction in volume of the gas or mixed gas and liquid hydrocarbons' during passage through the mass and which is the result of polymerization of its constituents. This is particularly desirable where the feed hydrocarbons are rich inolefins or polymerizable' constituents. Otherwise, the reduction in volume is quite substantial. A l.

The invention thus contemplates maintaining a 'substantially uniform velocity of hydrocarbons through all portions of the catalytic'mass.

multiple injection to the reaction vessel of re" cycled-hydrocarbons: that is', the gaseous or low- This. may be accomplished by multiple injection ofthe boiling hydrocarbons leaving the process and which have not been converted or have under-l gone incomplete conversion. Y Y

When employing multiple injection of the feed hydrocarbons and where the catalyst comprises phosphoric acid, it may be desirable to adjust or vary the water content of the hydrocarbons entering at each point of injection so as to regulate thev water 'content of the catalyst. y

An important objectof the invention is to maintain uniform temperature control 'throughout th'e catalyst mass. It is desirable to maintain the temperature o f'the mass within the range of about 380 F. to not' in excess' of about 475 F. l5

tendency for the temperature of th mass to increase substantially above the aforesaid temperatures. Higher temperatures, however, are objectionable, not only on account ofthe tendency to form liquid polymers'-c of higher boiling point than desired. but also on @account of the tendency to deposit a large amount of carbon or carbonaoeous matter upon the catalyst. z The operating temperature at which maximum olefinA conversion is obtained without excessive carbon deposition will vary with the olefin content of the gas. With a gas containing 40% of oleilns a temperature as high as 380 F. may -be permitted, while with ages containing 20% of oleflns the temperature may be as high as 450 F.

As the gaseous feed hydrocarbons pass downwardly through the catalyst bed there is a progressive reduction in olefin content, due to conversion to polymers, so that the temperature may with a temperature gradient throughout the cataJ 401yst tower and controlling the degree of this gradient by introduction of a portion of the cool fresh feed, or cooled recycled hydrocarbons, at various intermediate points in the tower. In

other words, it is desired to correlate the temperature at succeeding points inthe tower'with the olefin concentration at such points.

On the other hand, it is undesirable to maintion mass. since, under such conditions, the catalyst tends to absorb and retain more waterfrom the hydrocarbon feed and which results in softening of the catalyst. Close control of the temperature of the catalyst mas is also desirable from' the standpoint of 5I maintaining the proper equilibrium between the Since the reaction is exothermic there is a marked 'I'he invention therefore contemplates operating A tain too low a temperature throughout .the reacwater content of the catalyst and the water content of the gases undergoing treatment. In other words, at lower temperatures the catalyst picks up water, while at higher temperatures water is expelled. It is usually desirable, in the case of a catalyst comprising phosphoric acid, to operate with a concentration of around 100 to 110% HsPO4 by weight.

Advantageously, therefore, small amounts of water may be introduced at various points in the tower, with the amounts sointroduced being correlated with the temperature at the corresponding point within the tower to avoid dehydration or excessive hydration of the catalyst.

In order to describe the invention further reference willnow be lmade to the accompanying drawing showing an arrangement of ilow suitable for practicing the method of the invention.

Cracked naphtha, such as produced in the commercial cracking of petroleum, is drawn from a source not shown and passed through a pipe I to a. stabilizer 2, wherein the normally gaseous hydrocarbons, comprising both saturated and unsaturated hydrocarbons, are removed and withdrawn from the stabilizer through a pipe 3 leading to a condenser 4.

The condenser l discharges to a drum 5 in which liquid condensate collects. Uncondensed constituents, comprisingv xed gases, may be drawn off through a valved pipe 6. A portion of the condensate is returned by a pump 1 and pipe l to the upper portion of the stabilizer 2, and provides a reflux for controlling the extent of fractionation. I

-The surplus condensate or stabilizer reflux accumulating in the drum' 5 is drawn off through'a'v pipe 9 to a drum I 0 which provides a supply tank for the subsequent polymerizing operation.

The hydrocarbons accumulating in the drum III will comprise a substantial proportion of olefln hydrocarbons. The proportion of olefin hydrocarbons may range from around 20 to 40%, depending upon the nature of 'the cracked naphtha introduced to the-stabilizer 2. These hydrocarbons will comprise C4, Ca and C2 oleflns. These hydrocarbons are drawn oif through a pipe I I by a pump I2 and a portion thereof passed through a heater I3, wherein they are heated, under a pressure of around '100 pounds, to a temperature of about 375 to 400 F. -The heated hydrocarbons are passed through a pipe I4 to the upper portionof a reaction tower I5.

The tower I5 comprises a vertical lvessel packed with a catalyst inlump or granular form and arranged in a series of beds spaced vertically apart within the tower; The catalyst mayv comprise phosphoric acidV suspended -or supported upon quartz, pumice or clay, etc. The tower may contain around three or four beds, and each bed may range from about two to eight feet in depth.

As the olefin hydrocarbons pass through the beds in succession they are polymerized to form liquid polymers. As a result of heat evolution during polymerization the temperature of `each bed tends to rise.

A portion of the hydrocarbon feed is therefore by-passed around the heater through a pipe I6 and introduced through branch pipes I1 and I8 extending into the interior `of the tower in the spaces between the catalyst beds.

As indicated, the hydrocarbons passing through heat exchangers I`9 and 20, respectively, so as to within the catalyst tower. Ordinarily it may be suilicient to introduce these hydrocarbons at a temperature of around 90 to 100 F.

The proportion of the olefin-bearing hydrocarbon feed passing through the heater may comprise 80% by volume of the total charge, while the remaining 20% may be more or less equally divided between the pipes I1 and I8.

The reaction mixture comprising hydrocarbons and polymers is withdrawn from the bottom of the tower, either under its own pressure or by a pump 2I, and passed through a pipe 22 to a fractionator 23, wherein the more volatile hydrocarbons are separated from the liquid polymers. The liquid polymers are drawn o from the bottom of the fractionator through a pipe 24 and may be subjected to such further treatment as desired.

' If desired, the material from the bottom of the .be passed to the stabilizer or fractionator.

' The gaseous fraction removed from the top of \the fractionator through a pipe 25 will comprise saturated hydrocarbons, non-polymerized olei'lns and, if desired, partially polymerized'olen hydrocarbons. through a condenser 26 to a receiving drum 21. A portion of the condensate may be returned through a pipe 28 to provide a reflux in the top of the fractionator 23. Gaseous constituents may be drawn off through a pipe 29.

A portion of the surplus condensate collecting in the receiver 21 may be drawn of! by a pump 30 and passed through a pipe 3l communicating with pipes 32 and 33, by which means it is recycled 'through the polymerization tower. For example,

the recycled hydrocarbons may be conducted, all or in part, to the inlet of the heater I3, wherein they are mixed with fresh feedpassing through theheater and subsequently introduced at the top of the reaction tower.

On the other hand, the recycled hydrocarbons `may pass through the pipe 33, which communicates with pipe I6, previously referred to. In this way the recycled hydrocarbons are passed through pipes I1 and I8 to intermediate points of the reaction tower.

The recycled hydrocarbons entering pipe I6 may be at a temperature suitable for introduction to the intermediate points of the tower without further cooling or heating, although if such is necessary, it may be accomplished by means of the exchangers I9 and 20, to which reference has been made previously. Where the recycled hydrocarbons are thus returned to intermediate points of the reaction tower it may be unnecessary to use any of the fresh hydrocarbon feed as a cooling medium. In such case, the entire fresh hydrocarbon feed passes through the heater I3.

Duringpassage through the catalyst beds the initial volume of the feed-hydrocarbons will be to maintain a substantially uniform velocity of pipes I1 and I8 may be either heatedor cooled in l control more closelythe temperature'prevailing hydrocarbons through each of the catalyst beds within the tower. f

At ow velocities there is a tendency for heavy polymers to accumulate on the active surface of This distillate fraction is passed the catalyst, thereby greatly decreasing the conversion efficiency of the catalyst material.

' Increasing, the velocity, with the resulting sweeping action, tends to maintain the catalyst in an active condition. On the other hand, excessive velocities may be undesirable, since the sweeping action is then so great that inadequate contact of the reacting materials with the catalyst would be obtained. v In actual operation the reaction tower I and the fractionator 23 are maintained under supertop of the next bed to about 410 F. so that the temperature at .the bottom of' this second bed may be around 450 F.' The temperature at the top of the third bed may be maintained at around 430 F., while the temperature at the bottom of that bed may be around 475 F. Thus, there will be an overall temperature differential through the tower ofabout 50 or 60 F. v

As previously' mentioned, it is desirable to regulate Athe water content of the entering hydrocarbons. Thus, provision may be provided for introducing a small amount of waterto the heater inlet through a pipe 35 and to the pipes i1 and i8 through connections 36 and 31. For example, the water content of the hydrocarbons passing through'the heater i3may be around 0.3% by weight of the hydrocarbons. '-I'he water content of the hydrocarbons entering the tower through polymerization operation which is oi' exothermic character and which involves continuous removal of the polymerized material from the surface of the catalyst. f

The invention may be applied vwith such catalysts as copper pyrophosphate, phosphoric acid disposed on activated carbon, and catalysts comprising silica and alumina, or combinations of catalytic agents, such as activated lcarbon and copper pyrophosphate, -metallic oxides and pyrophosphates, etc.

It is contemplated, of course, that different catalysts will require different conditionsof temperature, pressureand velocity of ilow in order to realize optimum conditions.

In the foregoing description the feed to the polymerization unit has been described as the excess reflux condensate produced in the stabilization oi' cracked naphtha. It is contemplated that the feed stock may comprisean uncondensed gaseous fraction from the stabilizer accumulator drum 5. In this latter case the feed could be "charged in gaseous form'to the polymerization unit, or it may be compressed, cooled and condensed, and the condensate pumped as liquid to the o erization unit.

'I'lrilslyppllcation is a division of application Serial No. 284,192, filed July 13, 1939, for improvements in Catalytic conversion of hydrocarbons.

Obviously many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in thel appended claims.

I claim:

1..-A continuous method for polymerizing norl mally gaseous oleiins which comprises heating a stream of normally gaseous hydrocarbons containing about 20 to 40% olens to a temperature inthe range about 375 to 400 F., continuously introducing said feed stream in vapor phase to a reaction tower packed with a solid polymerization catalyst comprising phosphoric acid having Va concentration of about 100 to 110% HzPO4 by weight of the acid, passing said feed stream through the reaction tower from inlet to outlet,

veffecting polymerization of oleflnic constituents of the feed to normally liquid hydrocarbons during passage through the reaction tower from inlet to outlet, said polymerization being accompanied-by reduction in volume of said feed stream advancing through the reaction tower, injecting streams of hydrocarbon gas to the reaction tower at a plurality of succeeding points in the direction of hydrocarbon flow through the tower, adjusting the amount of gas so injected to compensate for said reduction in volume and thus maintain a substantially uniform velocity of hydrocarbon ow throughout the reaction tower from inlet to outlet, introducing a small amount of water in the feed hydrocarbon stream passing l to the inlet portion of the reaction tower, in-

'Jecting additional amounts of water to the reaction tower at a plurality of succeeding points in the direction of hydrocarbon flow such that the water content of the combined hydrocarbon stream passing through the outlet portion 'of the reaction tower is about 3% and maintaining the reaction temperature within the tower below about 475 F. l Y Y 2. A continuous method for polymerizing normally gaseous olefins which comprises heating a stream of normally gaseous hydrocarbons containing about 20 to 40% olens to a temperature in the range about 375 to 400 F., continuously introducing said feed stream in vapor phase to a reaction tower packed with a lsolid polymerization 'catalyst comprising phosphoric acid having aconcentration of about to 110% HaPO4 by weight of the acid, passing said feed stream through the reaction tower from inlet to outlet.

effecting polymerization of oleiinic constituents of thefeed to normally liquid hydrocarbons fluring passage through the reaction tower from in-y let to outlet, said polymerization being accompanied by reduction in volume of said feed stream advancing through the reaction tower, injecting streams of hydrocarbon gas to the reaction tower temperature of said streams of gas passing to succeeding points in the reaction tower, and

maintaining the reaction temperature within th `reaction tower below about 475 F.

3. A continuous method for polymerizing normally gaseous oleflns which comprises heating a eiecting polymerization of olenic constituents of the feed to normally liquid hydrocarbons during passage through the reaction tower from inlet to outlet, said polymerization being accompanied by reduction in volume of said feed stream advancing through the reaction tower, injecting streams of hydrocarbon -gas to the reaction tower at a plurality of succeeding points in the direc- Y tion of hydrocarbon flow through the tower, ad-

justing the amount of gas so injected to com-l pensate for said reduction in volume and thus `maintain a substantially uniform velocity of hydrocarbon flow throughout the reaction tower from inlet to outlet, introducing a small amount of water in the feed hydrocarbon stream passing to the inlet portion of the reaction tower, injecting additional amounts of water to the reaction tower at a. plurality of succeeding pointsl in the direction of hydrocarbon flow such that the water content of the combined hydrocarbon stream passing through the outlet portion of the reaction tower is about 3%, separately adjusting the temperature of said streams oi.' gas passing to succeeding points in the reaction tower, and maintaining the reaction temperature within the reaction tower below about 475 F. LEBBEUS C. KEMP.- 

